EP0581390B1 - Crop protection concentrate - Google Patents
Crop protection concentrate Download PDFInfo
- Publication number
- EP0581390B1 EP0581390B1 EP93202252A EP93202252A EP0581390B1 EP 0581390 B1 EP0581390 B1 EP 0581390B1 EP 93202252 A EP93202252 A EP 93202252A EP 93202252 A EP93202252 A EP 93202252A EP 0581390 B1 EP0581390 B1 EP 0581390B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- crop protection
- range
- paraffinic
- paraffinic oil
- antifoam
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000012141 concentrate Substances 0.000 title claims abstract description 23
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 44
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 44
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 27
- 239000010690 paraffinic oil Substances 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims description 37
- 238000009472 formulation Methods 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 8
- 239000012188 paraffin wax Substances 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 6
- XWPZUHJBOLQNMN-UHFFFAOYSA-N metconazole Chemical group C1=NC=NN1CC1(O)C(C)(C)CCC1CC1=CC=C(Cl)C=C1 XWPZUHJBOLQNMN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011814 protection agent Substances 0.000 claims description 4
- 239000005868 Metconazole Substances 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 239000002518 antifoaming agent Substances 0.000 abstract description 42
- 239000003795 chemical substances by application Substances 0.000 abstract description 15
- 239000004094 surface-active agent Substances 0.000 abstract description 9
- 239000002671 adjuvant Substances 0.000 abstract description 6
- 239000006260 foam Substances 0.000 description 15
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 14
- 239000003921 oil Substances 0.000 description 12
- 238000005187 foaming Methods 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- 239000004480 active ingredient Substances 0.000 description 7
- 238000010790 dilution Methods 0.000 description 6
- 239000012895 dilution Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 5
- 239000002283 diesel fuel Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003208 petroleum Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000003254 anti-foaming effect Effects 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 3
- 239000012669 liquid formulation Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- 239000003849 aromatic solvent Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007182 Ochroma pyramidale Species 0.000 description 1
- 235000005013 Pinus cembroides Nutrition 0.000 description 1
- 235000008575 Pinus pinea Nutrition 0.000 description 1
- 240000007789 Pinus pinea Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000240 adjuvant effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 1
- DFBKLUNHFCTMDC-PICURKEMSA-N dieldrin Chemical compound C([C@H]1[C@H]2[C@@]3(Cl)C(Cl)=C([C@]([C@H]22)(Cl)C3(Cl)Cl)Cl)[C@H]2[C@@H]2[C@H]1O2 DFBKLUNHFCTMDC-PICURKEMSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000004495 emulsifiable concentrate Substances 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 239000010665 pine oil Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 150000003138 primary alcohols Chemical group 0.000 description 1
- 239000010499 rapseed oil Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000004334 sorbic acid Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000004546 suspension concentrate Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000001993 wax Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
Definitions
- the present invention relates to a crop protection concentrate and its use in a method for preparing a crop protection formulation.
- antifoaming agents have antifoam components, such as silicone-based products, e.g. silicone-coated silica particles, hydrocarbon waxes, or fatty amides or esters, often with a carrier such as a hydrocarbon oil, and if necessary an emulsifier component.
- treatment formulations are often sold in concentrated forms for dilution with water by the farmer or user at the site of use.
- surfactants are often incorporated into the treatment concentrates and foaming can occur on mixing with water in a spray tank.
- a small amount of foaming is acceptable, but largescale foaming can give spraying problems.
- diesel oil is added to destabilise the foam. This practice is undesirable as it leads to crop, and other areas, being sprayed with unrefined fuel oils which is unacceptable from the environmental viewpoint.
- Hydrocarbon (e.g. paraffin) oils are also known as anti-foaming additives for formulations of crop protection agents, e.g. from EP-A-0498231 and (East) German Patentschrift 215227.
- paraffinic oils can significantly destabilise foam formed in crop protection formulations on dilution in water.
- time taken to break the foam with these paraffinic oils is significantly shorter than that found for conventional antifoam agents and for diesel oil.
- paraffinic oils of the lubricant oil type such as the oil available from SHELL under the trade name HVI 60
- HVI 60 is known to be useful in crop protection formulations because of their adjuvant effect by which the activity of an active ingredient is enhanced, permitting the use of smaller quantities of the active ingredient to be used.
- EP-A-356812 discloses an adjuvant composition which comprises surfactant components and optionally a hydrocarbon component.
- the latter is preferably an aromatic solvent but may be a paraffinic oil or solvent, suitably a solvent-refined petroleum oil fraction composed of paraffinic and naphthenic hydrocarbons and generally having a flash point in excess of 200 deg C.
- the hydrocarbon component is believed to exert a minor biochemical effect in use but no antifoaming action is noted, indeed low-foaming surfactants are specifically required for the adjuvant composition.
- Paraffinic hydrocarbon oils of the type found herein to be useful as antifoam agents have been used in domestic situations because of their low odour and solvent properties, for example SHELLSOL D70 is used as the inert carrier solvent for the insecticide spray SHELLTOX, and have been found to be acceptable by the regulatory authorities.
- paraffinic oils specified in the present invention may of course be utilised for any antifoaming situation where the paraffinic component fulfills any regulatory requirements and is compatible with the process followed and product prepared.
- an agent which prevents foaming from occurring or controls or removes a foam after formation includes an agent which prevents foaming from occurring or controls or removes a foam after formation.
- the present invention provides a crop protection concentrate comprising a crop protection agent, an alcohol ethoxylate and a paraffinic oil wherein the paraffinic oil comprises in the range of from 45 to 100%, preferably 50 to 100%, mass by mass of one or more paraffinic hydrocarbon(s) and has an average molecular weight in the range of from 100 to 200, preferably 140 to 170, and the weight ratio of alcohol ethoxylate to paraffinic oil in the concentrate is in the range of from 11:1 to 1:1.
- paraffinic oil is used herein to denote a hydrocarbon which is a paraffin or a hydrocarbon mixture having a paraffinic component, which is usually derived from petroleum sources.
- the hydrocarbon(s) may be derived by catalytic hydrogenation of a petroleum fraction, or be obtained by distillation, for example of hydrocarbon reaction products.
- paraffinic hydrocarbons are a mix of paraffin components with a minor amount (less than 0.1% m/m, preferably less than 0.03 % m/m) of aromatics; naphthenic components may also be present.
- the flash point of the required hydrocarbon or hydrocarbon mix is less than 100 deg C, and preferably lies in the range of from 35 to 75 deg C.
- the paraffinic hydrocarbon oil specified in the present invention may therefore be used as a pure or substantially pure paraffin, e.g. decane, a mixture of paraffinic isomers, a mixture of paraffins or as a mixture of paraffins with naphthenic or aromatic hydrocarbons.
- the paraffinic component may be present as paraffin(s) or as isoparaffin(s) and generally herein the term paraffin should be understood to include isoparaffin.
- the paraffinic hydrocarbon oil contains one or more paraffins having in the range of from 9 to 14 carbon atoms, especially from 10 to 14 carbon atoms.
- Especially suitable paraffinic hydrocarbon oils have a density at 15 deg C (ASTM D 1298) in the range of from 0.70 to 0.85 kg/l, especially in the range of from 0.75 to 0.80 kg/l.
- Useful paraffinic oils are the range of paraffinic and isoparaffinic hydrocarbons available in the SHELLSOL range of hydrocarbon solvents available from Shell, or the equivalent products, for example the ISOPAR product range available from Exxon. Preferred are the SHELLSOL D and SHELLSOL T hydrocarbon grades or equivalents.
- the preferred SHELLSOL D grades may be defined as a complex combination of hydrocarbons obtained by treating a petroleum fraction with hydrogen in the presence of a catalyst, consisting of hydrocarbons predominantly in the range C 9 to C 14 and boiling in the range of from approximately 155 deg C to 250 deg C.
- the aromatic content is below 0.03 % m/m and the flash point is not less than 38 deg C.
- Preferred forms have a characteristically low, sweet odour.
- the preferred SHELLSOL T grades may be defined as a complex combination of hydrocarbons produced by distillation of the reaction products of isobutane with monoolefinic hydrocarbons, consisting of predominantly branched chain saturated hydrocarbons having carbon numbers in the range of from C 10 to C 12 and boiling in the range of approximately 167 deg C to 218 deg C. Preferred forms have a characteristically low odour.
- the specified paraffinic hydrocarbons are of particular use in conjunction with crop protection formulations when a crop protection concentrate is diluted in water or an aqueous medium.
- the crop protection concentrate may be in the form of a soluble liquid, emulsifiable concentrate, emulsion concentrate or a suspension concentrate. It is a significant departure from conventional practice to include an antifoam component into such crop protection formulations.
- the alcohol ethoxylates are suitably derived from a C 9-18 , preferably a C 9-15 , aliphatic alcohol.
- the ethoxylate chain suitably has at least 5 ethoxy moieties, preferably from 5 to 9 ethoxy moieties.
- the DOBANOL range of alcohol ethoxylates available from Shell and the GENAPOL range of alcohol ethoxylates available from Hoechst may be particularly mentioned.
- the amount of ethoxylate present in a crop protection concentrate of the present invention lies in the range of from 500 to 600 g/l, especially 400g/l, and the paraffinic oil is present in an amount in the range of from 50 to 300 g/l, especially 200g/l.
- the present invention further provides a method for preparing a crop protection formulation comprising adding a crop protection concentrate as defined above to water.
- Example 1 The active ingredient used for all of the Examples was the compound 1-(4-chlorobenzyl)-3,3-dimethyl-2-hydroxy-2-(1,2,4-triazol-1-yl)-methylcyclopentane, commonly known as metconazole.
- Example 1 is a comparison example; Examples 2 and 3 show the use of specified paraffinic oils as antifoaming agents. In the Examples "% m/m" indicates a mass by mass percentage basis.
- the antifoam activity of a number of conventional antifoam agents and hydrocarbon oils was assessed using the following soluble liquid formulation: Active ingredient 60g. DOBANOL 91-6 600g. amyl alcohol to 1 L.
- DOBANOL 91-6 is an alcohol ethoxylate from SHELL which has C 9-11 primary alcohol moieties with an average of 6 ethoxy units per molecule.
- ANTIFOAM AGENT CONCENTRATION (g/l) TIME TO ACHIEVE FOAM BREAK - - 21 min 10 sec ANTIFOAM T 5 24 min 14 sec ANTIFOAM T 10 23 min 22 sec ANTIFOAM T 20 22 min 53 sec ANTIFOAM T 30 17 min 18 sec ANTIFOAM DN 5 > 21 min ANTIFOAM DNE 5 > 21 min ANTIFOAM FN 1 > 21 min ANTIFOAM TIP 1 > 21 min ANTIFOAM KN 1 > 21 min BEVALOID 642 1 > 21 min BAYSILONE 0.5 12 min 00 sec Diesel oil 5 13 min 21 sec SHELLSOL E 200 > 21 min HVI 60 200 > 21 min ANTIFOAM T, ANTIFOAM DN, ANTIFOAM DNE and BAYSILONE are all antifoam agents available from Bayer AG.
- ANTIFOAM FN, ANTIFOAM TIP and ANTIFOAM KN are all antifoam agents available from Hoechst.
- BEVALOID 642 is an antifoam agent available from Rhone-Poulenc.
- SHELLSOL E is an aromatic hydrocarbon available from SHELL which typically contains 83 (ASTMD 1319 %v/v) aromatics, 12 %m/m paraffins and 4 %m/m naphthenics, and has a density at 15 deg C of 0.856 kg/l (ASTM D 1298), an average molecular weight of 125, and a flash point (ABEL) of 42 deg C. It distills between 164 deg C and 188 deg C.
- HVI 60 is a paraffinic oil adjuvant available from SHELL, which typically contains in the range of from 10 to 30 % aromatics, and has a flash point of 204 deg C by PMcc, and a specific gravity of 0.872.
- each antifoam agent used was determined in accordance with the manufacturer's recommendations. For ANTIFOAM T, no more than 30g/l could be dissolved in the test formulation; similarly for others of the antifoam agents listed, the concentration quoted is the maximum amount that could be incorporated into the test formulation.
- oils were tested for antifoam properties with the test formulation but were found to have no ability to break the foam formed on dilution with water: SHELL GRAVEX oil (various grades), stone-pine oil, rape oil, balsa oil and solvent naphtha. Also a number alcohols were tested and showed no antifoam action: methanol, ethanol, decanol, cyclohexanol, heptanol, octanol and benzylalcohol, amongst others.
- SHELLSOL D 70 from Shell is a combination of paraffinic hydrocarbons, which typically contains in the range of from 49 to 60 % m/m C 11-14 paraffins, in the range of from 40 to 51 % m/m naphthenics, less than 5 % m/m benzene and 0.03 % m/m aromatics, and has a density (ASTM D 1298) at 15 deg C of 0.792 kg/l, an average molecular weight of 174, a flash point (ABEL) of 73 deg C (ASTM D 93 PMcc), and a boiling range of from 190 to 250 deg C.
- paraffinic hydrocarbons act very quickly to break the foam formed on dilution and mixing with water.
- the antifoam activity of a number of paraffinic hydrocarbons was assessed using a number of metconazole/DOBANOL 91-6/amyl alcohol soluble liquid formulations using the following test method.
- SHELLSOL D60 from Shell is a combination of paraffinic hydrocarbons, which typically contains in the range of from 46 to 55 % m/m C 10-12 paraffins, in the range of from 45 to 54 % m/m naphthenics, less than 5 % m/m benzene and 0.02 % m/m aromatics, and has a density at 15 deg C (ASTM D 1298) of 0.786 kg/l, a flash point (ABEL) of 66 (ASTM D 93 PMcc), an average molecular weight of 154, and a boiling range of from 178 to 212 deg C.
- SHELLSOL D40 from Shell is a combination of paraffinic hydrocarbons, which typically contains in the range of from 50 to 60 % m/m C 9-11 paraffins, in the range of from 40 to 50 % m/m naphthenics, less than 5 % m/m benzene and 0.02 % m/m aromatics, and has a density at 15 deg C ( ASTM D 1298) of 0.765 kg/l, a flash point (ABEL) of 40, an average molecular weight of 141, and a boiling range of from 155 to 202 deg C.
- paraffinic hydrocarbons typically contains in the range of from 50 to 60 % m/m C 9-11 paraffins, in the range of from 40 to 50 % m/m naphthenics, less than 5 % m/m benzene and 0.02 % m/m aromatics, and has a density at 15 deg C ( ASTM D 1298) of 0.765 kg/l, a
- SHELLSOL TD is an isoparaffinic hydrocarbon from SHELL which typically contains greater than 99 % m/m C 10-11 paraffins, 0 % m/m naphthenics, and 0.01 % m/m aromatics, and has a density at 15 deg C (ASTM D 1298) of 0.751 kg/l, a flash point (ABEL) of 44, an average molecular weight of 164, and a boiling range of from 167 to 195 deg C.
- SHELLSOL T is an isoparaffinic hydrocarbon from SHELL which typically contains greater than 99 % m/m C 11-12 paraffins, 0 % m/m naphthenics, and 0.01 % m/m aromatics, and has a density at 15 deg C (ASTM D 1298) of 0.761 kg/l, a flash point (ABEL) of 60 (DIN EN 57), an average molecular weight of 169, and a boiling range of from 179 to 218 deg C.
- the test formulations used were as follows: C D Active ingredient 60g. 60g. DOBANOL 91-6 400g. 450g. paraffinic hydrocarbon 200g. 200g. amyl alcohol to 1 L. to 1 L.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Dispersion Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Degasification And Air Bubble Elimination (AREA)
- Medicines Containing Plant Substances (AREA)
- Treatment And Processing Of Natural Fur Or Leather (AREA)
- Saccharide Compounds (AREA)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP93202252A EP0581390B1 (en) | 1992-07-30 | 1993-07-29 | Crop protection concentrate |
GR20000401602T GR3033917T3 (en) | 1992-07-30 | 2000-07-07 | Antifoaming agents. |
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP92113064 | 1992-07-30 | ||
EP92113064 | 1992-07-30 | ||
EP93202252A EP0581390B1 (en) | 1992-07-30 | 1993-07-29 | Crop protection concentrate |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0581390A2 EP0581390A2 (en) | 1994-02-02 |
EP0581390A3 EP0581390A3 (es) | 1994-04-13 |
EP0581390B1 true EP0581390B1 (en) | 2000-04-12 |
Family
ID=8209858
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP93202252A Expired - Lifetime EP0581390B1 (en) | 1992-07-30 | 1993-07-29 | Crop protection concentrate |
Country Status (8)
Country | Link |
---|---|
US (1) | US6297413B1 (es) |
EP (1) | EP0581390B1 (es) |
AT (1) | ATE191656T1 (es) |
DE (1) | DE69328327T2 (es) |
DK (1) | DK0581390T3 (es) |
ES (1) | ES2147191T3 (es) |
GR (1) | GR3033917T3 (es) |
PT (1) | PT581390E (es) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2838120B1 (fr) * | 2002-04-04 | 2004-06-11 | Chryso Sas | Compositions de cure de mortiers ou betons assurant la retention d'eau(pendant la prise) et procede de mise en oeuvre |
AR043292A1 (es) * | 2002-04-25 | 2005-07-27 | Shell Int Research | Uso de gasoil derivado de fischer-tropsch y una composicion combustible que lo contiene |
JP5390748B2 (ja) * | 2003-09-03 | 2014-01-15 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | 燃料組成物 |
JP5390747B2 (ja) * | 2003-09-03 | 2014-01-15 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | フィッシャー・トロプシュ誘導燃料を含有する燃料組成物 |
US7662757B2 (en) * | 2006-06-27 | 2010-02-16 | Exxonmobil Research And Engineering Company | Stable defoamant composition containing GTL fluid and/or hydrodewaxate and/or hydroisomerized/catalytic (and/or solvent) dewaxed fluid as diluent |
AR069052A1 (es) * | 2007-10-30 | 2009-12-23 | Shell Int Research | Mezclas para utilizar en composiciones de combustible |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1769543C2 (de) * | 1968-06-07 | 1982-06-03 | Basf Ag, 6700 Ludwigshafen | Schaumverhüter für wäßrige Systeme |
US3657136A (en) * | 1969-12-29 | 1972-04-18 | Betz Laboratories | Method of controlling foam in acrylonitrile production |
US4221600A (en) * | 1978-02-02 | 1980-09-09 | Westvaco Corporation | Liquid defoaming composition |
DD215227B1 (de) * | 1983-04-13 | 1988-02-17 | Bitterfeld Chemie | Verfahren zur herstellung stabiler suspensionskonzentrate fungizider wirkstoffe |
GB9102757D0 (en) * | 1991-02-08 | 1991-03-27 | Albright & Wilson | Biocidal and agrochemical suspensions |
GB9116557D0 (en) * | 1991-07-31 | 1991-09-11 | Shell Int Research | Fungicidal compositions |
-
1993
- 1993-07-27 US US08/097,801 patent/US6297413B1/en not_active Expired - Lifetime
- 1993-07-29 PT PT93202252T patent/PT581390E/pt unknown
- 1993-07-29 AT AT93202252T patent/ATE191656T1/de active
- 1993-07-29 EP EP93202252A patent/EP0581390B1/en not_active Expired - Lifetime
- 1993-07-29 DK DK93202252T patent/DK0581390T3/da active
- 1993-07-29 DE DE69328327T patent/DE69328327T2/de not_active Expired - Lifetime
- 1993-07-29 ES ES93202252T patent/ES2147191T3/es not_active Expired - Lifetime
-
2000
- 2000-07-07 GR GR20000401602T patent/GR3033917T3/el unknown
Also Published As
Publication number | Publication date |
---|---|
US6297413B1 (en) | 2001-10-02 |
EP0581390A3 (es) | 1994-04-13 |
ATE191656T1 (de) | 2000-04-15 |
ES2147191T3 (es) | 2000-09-01 |
GR3033917T3 (en) | 2000-11-30 |
DE69328327T2 (de) | 2000-08-24 |
DK0581390T3 (da) | 2000-07-03 |
DE69328327D1 (de) | 2000-05-18 |
PT581390E (pt) | 2000-08-31 |
EP0581390A2 (en) | 1994-02-02 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US4880557A (en) | Spray Lustering-cleansing agent | |
AU689610B2 (en) | Ammonium bicarbonate/ammonium carbamate activated benzyl alcohol paint stripper | |
EP1305086B1 (en) | Aqueous foamable concentrates and methods | |
US6168702B1 (en) | Chemical demulsifier for desalting heavy crude | |
JPH10506942A (ja) | アスファルト剥離剤と使用方法 | |
ZA200509181B (en) | Emulsified FCC feedstock for improved spray atomization | |
US6228239B1 (en) | Crude oil desalting method | |
EP0581390B1 (en) | Crop protection concentrate | |
US4655959A (en) | Preparation of non-flammable aerosol propellant microemulsion system | |
JPH07233001A (ja) | エアゾール組成物 | |
EP0860203A2 (en) | Chemical dispersant for oil spills | |
US4087398A (en) | Antifoam compositions | |
US5085849A (en) | d-Limonene containing space or room aerosol deodorant | |
IE44071B1 (en) | Compositions and processes for the dispersing of oil spillages | |
Canevari | General dispersant theory | |
RU2167522C2 (ru) | Жидкое пестицидное средство в виде эмульсии масло-в-воде | |
GB2244279A (en) | Fluorosilicone anti-foam additive | |
US4407741A (en) | Hydrotropic cleaner | |
EP0959983B1 (en) | Dispersant formulation for cleaning up oil spills | |
AU715680B2 (en) | Release agent for rolls and method for improving release properties of rolls | |
GB2231284A (en) | Hydrocarbon dispersions in water | |
JP2001220574A (ja) | 自己攪拌型流出油処理剤 | |
CN102247712B (zh) | 消泡剂及使用它的制品和方法 | |
JP3118080B2 (ja) | 低泡性樹脂エマルション組成物 | |
CA1207217A (en) | Paint detackification using oil-in-water emulsions |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
AK | Designated contracting states |
Kind code of ref document: A2 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE |
|
PUAL | Search report despatched |
Free format text: ORIGINAL CODE: 0009013 |
|
AK | Designated contracting states |
Kind code of ref document: A3 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE |
|
17P | Request for examination filed |
Effective date: 19941004 |
|
17Q | First examination report despatched |
Effective date: 19950421 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
RTI1 | Title (correction) |
Free format text: CROP PROTECTION CONCENTRATE |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE CH DE DK ES FR GB GR IE IT LI LU MC NL PT SE |
|
REF | Corresponds to: |
Ref document number: 191656 Country of ref document: AT Date of ref document: 20000415 Kind code of ref document: T |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: NV Representative=s name: A. BRAUN, BRAUN, HERITIER, ESCHMANN AG PATENTANWAE Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 69328327 Country of ref document: DE Date of ref document: 20000518 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: DK Ref legal event code: T3 |
|
ITF | It: translation for a ep patent filed | ||
REG | Reference to a national code |
Ref country code: PT Ref legal event code: SC4A Free format text: AVAILABILITY OF NATIONAL TRANSLATION Effective date: 20000608 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2147191 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PFA Owner name: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. Free format text: SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.#CAREL VAN BYLANDTLAAN 30#2596 HR DEN HAAG (NL) -TRANSFER TO- SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.#CAREL VAN BYLANDTLAAN 30#2596 HR DEN HAAG (NL) |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20110801 Year of fee payment: 19 Ref country code: DK Payment date: 20110801 Year of fee payment: 19 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: LU Payment date: 20120727 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: SE Payment date: 20120731 Year of fee payment: 20 Ref country code: IE Payment date: 20120723 Year of fee payment: 20 Ref country code: MC Payment date: 20120727 Year of fee payment: 20 Ref country code: GB Payment date: 20120731 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GR Payment date: 20120725 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20120725 Year of fee payment: 20 Ref country code: BE Payment date: 20120831 Year of fee payment: 20 Ref country code: ES Payment date: 20120829 Year of fee payment: 20 Ref country code: FR Payment date: 20120814 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20120727 Year of fee payment: 20 Ref country code: DE Payment date: 20121001 Year of fee payment: 20 Ref country code: PT Payment date: 20120130 Year of fee payment: 20 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: AT Payment date: 20120726 Year of fee payment: 20 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R071 Ref document number: 69328327 Country of ref document: DE |
|
BE20 | Be: patent expired |
Owner name: *SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V. Effective date: 20130729 |
|
REG | Reference to a national code |
Ref country code: DK Ref legal event code: EUP |
|
REG | Reference to a national code |
Ref country code: PT Ref legal event code: MM4A Free format text: MAXIMUM VALIDITY LIMIT REACHED Effective date: 20130729 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: V4 Effective date: 20130729 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: PE20 Expiry date: 20130728 |
|
REG | Reference to a national code |
Ref country code: SE Ref legal event code: EUG |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK07 Ref document number: 191656 Country of ref document: AT Kind code of ref document: T Effective date: 20130729 |
|
REG | Reference to a national code |
Ref country code: GR Ref legal event code: MA Ref document number: 20000401602 Country of ref document: GR Effective date: 20130730 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20130730 Ref country code: PT Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20130806 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20130728 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MK9A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20130729 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20140925 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF EXPIRATION OF PROTECTION Effective date: 20130730 |